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| United States Patent |
5,310,794
|
|
DeNicola, Jr.
, et al.
|
May 10, 1994
|
Theromoplastic blends containing graft copolymers of polyacrylates as
impact modifiers
Abstract
Disclosed are blends comprising a propylene polymer material grafted with a
polymerizable monomer(s) of a polymer(s) having a Tg greater than
80.degree. C., a propylene polymer material grafted with a polymerizable
monomer(s) of a polymer(s) having a Tg less than 20.degree. C., and
optionally at least one other rubber modifier.
| Inventors:
|
DeNicola, Jr.; Anthony J. (Newark, DE);
Giroux; Thomas A. (Bear, DE)
|
| Assignee:
|
Himont Incorporated (Wilmington, DE)
|
| Appl. No.:
|
860864 |
| Filed:
|
March 31, 1992 |
| Current U.S. Class: |
525/71; 525/70; 525/80; 525/98; 525/228; 525/240; 525/241 |
| Intern'l Class: |
C08L 051/06; C08L 053/02 |
| Field of Search: |
525/80,71,70,301
|
References Cited
U.S. Patent Documents
| 3314904 | Apr., 1967 | Burkus | 525/71.
|
| 4537933 | Aug., 1985 | Walker et al. | 525/71.
|
| 4560725 | Dec., 1985 | Van Bokhoven et al. | 525/67.
|
| 4704431 | Nov., 1987 | Stuart et al. | 525/75.
|
| 4849473 | Jul., 1989 | Cigna et al. | 525/86.
|
| 4937280 | Jun., 1990 | Biglione | 524/504.
|
| 4957974 | Sep., 1990 | Ilenda et al. | 525/70.
|
| 4990558 | Feb., 1991 | DeNicola, Jr. et al. | 524/504.
|
Primary Examiner: Seidleck; James J.
Assistant Examiner: Warzel; M. L.
Claims
We claim:
1. A thermoplastic blend consisting essentially of, by weight (A) 30 to 90%
of a propylene polymer material grafted with a polymerizable monomer(s) of
a polymer(s) having a Tg greater than 80.degree. C. and polymerized
monomer(s) content of 5 to 70% selected from the group consisting of
styrene, styrene/methyl methacrylate, styrene/methacrylic acid and
styrene/acrylonitrile and (B) 10% to 70% of propylene polymer material
grafted with a polymerizable monomer(s) of a polymer(s) having a Tg less
than 20.degree. C. and a polymerized monomer content of 5 to 50% selected
from the group consisting of butyl acrylate, butylacrylate/butyl
methacrylate and butyl acrylate/ethylhexyl acrylate.
2. The blend of claim 1, wherein said propylene material is selected from
the group consisting of a homopolymer of propylene, a random copolymer of
propylene and an olefin selected from ethylene and C.sub.4 -C.sub.10
alpha-olefins having a maximum polymerized ethylene content of about 10%
and maximum polymerized C.sub.4 -C.sub.10 alpha-olefin content of about
20%, and a random terpolymer of propylene with two alpha-olefins selected
from the group consisting of ethylene and C.sub.4 -C.sub.8 alpha-olefin
having a maximum polymerized C.sub.4 -C.sub.8 alpha-olefin content of
about 20%, and when ethylene is present a maximum polymerized ethylene
content of about 5%.
3. The blend of claim 1, wherein the polymerizable monomer is butyl
acrylate.
4. The blend of claim 1, wherein (A) is a graft copolymer of styrene on a
polypropylene backbone and (B) is a graft copolymer of butyl acrylate on a
polypropylene backbone.
5. The blend of claim 1, wherein (A) is a graft copolymer of styrene on a
polypropylene backbone and (B) is a graft copolymer of butyl
acrylate/butyl methacrylate on a polypropylene backbone.
6. The blend of claim 1, wherein (A) is a graft copolymer styrene/methyl
methacrylate on a polypropylene backbone and (B) is a graft copolymer of
butyl acrylate on a polypropylene backbone.
7. The blend of claim 1, wherein (A) is a graft copolymer of styrene/methyl
methacrylate on a polypropylene backbone and (B) is a graft copolymer of
butyl acrylate/butyl methacrylate on a polypropylene backbone.
8. The blend of claim 1, wherein (A) is a graft copolymer of
styrene/acrylonitrile on a polypropylene backbone and (B) is a graft
copolymer of butyl acrylate on a polypropylene backbone.
9. The blend of claim 1, wherein (A) is a graft copolymer of
styrene/acrylonitrile on a polypropylene backbone and (B) is a graft
copolymer of butyl acrylate/butyl methacrylate on a polypropylene
backbone.
10. A thermoplastic blend consisting essentially of, by weight, (A) 30 to
90% of a propylene polymer material grafted with a polymerizable
monomer(s) of a polymer(s) having a Tg greater than 80.degree. C. and
polymerized monomer(s) content of 5 to 70% selected from the group
consisting of styrene, styrene/methyl methacrylate, styrene/methacrylic
acid and styrene/acrylonitrile, (B) 10 to 70% of propylene polymer
material grafted with a polymerizable monomer(s) of a polymer(s) having a
Tg less than 20 .degree. C. and a polymerized monomer content of 5 to 50%
selected from the group consisting of butyl acrylate, butylacrylate/butyl
methacrylate and butyl acrylate/ethylhexyl acrylate and (c) 5 to 20% of at
least one other rubber modifier, wherein the total amount of (B)+(C) is
from 10 to 70% by weight based on the total blend.
11. The blend of claim 10, wherein said propylene polymer material is
selected from the group consisting of a homopolymer of propylene, a random
copolymer of propylene and an olefin selected from ethylene and C.sub.4
-C.sub.10 alpha-olefins having a maximum polymerized ethylene content of
about 10% and a maximum polymerized C.sub.4 -C.sub.10 alpha-olefin content
of about 20%, and a random terpolymer of propylene with two alpha-olefins
selected from the group consisting of ethylene and C.sub.4 -C.sub.8
alpha-olefin having a maximum polymerized C.sub.4 -C.sub.8 alpha-olefin
content of about 20%, and when ethylene is present a maximum polymerized
ethylene content of about 5%.
12. The blend of claim 13, wherein said at least one other rubber modifier
is selected from the group consisting of (i) an olefin rubber containing 2
or more monomers selected from ethylene, propylene or butene, and
optionally a non-conjugated diene, (ii) one or more monoalkenyl aromatic
hydrocarbon-conjugated diene block copolymer of hydrogenated products
thereof having a number average molecular weight of from 45,000 to 260,000
and monoalkenyl aromatic hydrocarbon monomer content of from 5 to 50% and
mixtures of (i) and (ii).
13. The blend of claim 10, wherein (A) is a graft copolymer of styrene on a
polypropylene backbone, (B) is a graft copolymer of butyl acrylate on a
polypropylene backbone and (c) is an ethylene/propylene copolymer rubber.
14. The blend of claim 10, wherein (A) is a graft copolymer of styrene on a
polypropylene backbone, (B) is a graft copolymer of butyl acrylate on a
polypropylene backbone and (C) is hydrogenated styrene/butadiene/styrene
block copolymer.
15. The blend of claim 10, wherein (A) is present in an amount of from 45
to 80%, (B) is present in an amount of from 15 to 45% and (C) is present
in an amount of from 5 to 10%.
16. The blend of claim 10, wherein (A) is a graft copolymer of
styrene/acrylonitrile on a polypropylene backbone, (B) is a graft
copolymer of butyl acrylate on a polypropylene backbone and (C) is a
hydrogenated styrene/butadiene/styrene block copolymer.
17. The blend of claim 10, wherein (A) is a graft copolymer of
styrene/acrylonitrile on a polypropylene backbone, (B) is graft copolymer
of butyl acrylate on a polypropylene backbone and (C) is an
ethylene/propylene copolymer rubber.
Description
FIELD OF THE INVENTION
This invention relates to blends comprising (A) a propylene polymer
material grafted with a polymerizable monomer(s) of a polymer(s) having a
Tg greater than 80.degree. C., (B) propylene polymer material grafted with
a polymerizable monomer(s) of a polymer(s) having a Tg of less than
20.degree. C., and optionally at least one other rubber modifier.
BACKGROUND OF THE INVENTION
Typically, graft copolymers of olefin polymer materials have been impact
modified with ethylene/propylene copolymer rubber,
ethylene/propylene/diene monomer rubber, and ASA polymers. For example,
U.S. Pat. No. 3,314,904 describes forming a "gum plastic" by making a
graft copolymer of styrene on polyethylene or polypropylene, and, in
particular, a graft interpolymer of styrene, acrylonitrile, and
polyethylene or polypropylene, and blending the graft copolymer with
certain selected compatible rubbery materials. The grafted styrene or
styrene/acrylonitrile content of the graft copolymer is 75-95%, preferably
85-95%, and more preferably 90-95%. Hence the graft copolymer is
predominantly bound styrene or bound styrene/acrylonitrile, and in the
graft copolymers made from polypropylene, the polypropylene is only a
minor component and present as a dispersed phase. Thus the properties of
the bound styrene or styrene/acrylonitrile predominate. The graft
copolymer is made by subjecting the polyolefin to high-energy ionizing
radiation, and then contacting the irradiated polyolefin with styrene or
with styrene and acrylonitrile.
U.S. Pat. No. 4,537,933 discloses a blend of a polyolefin graft polymer,
preferably a polyvinyl halide polyolefin graft polymer, and an ASA
polymer. The ASA polymer is a copolymer of styrene and acrylonitrile (SAN)
that is modified with an acrylate polymer, a chlorinated polyethylene or
an olefin-diolefin modified polymer, such as an ethylene/propylene polyene
modified polymer. The ASA polymer modified with the olefin-diolefin
modified polymer has a styrene/acrylonitrile content of 60-95%. The
properties of the SAN predominate since the rubber is only a minor
component and present as a dispersed phase. Also, the matrix phase of the
polymeric components must be miscible.
SUMMARY OF THE INVENTION
It has now been found that rigid graft copolymers comprising a propylene
polymer material backbone having graft polymerized thereon a monomer(s) of
a rigid polymer(s), a polymer having a glass transition temperature (Tg)
of greater than 80.degree. C., can be impact modified by blending said
rigid graft copolymers with a graft copolymer comprising a propylene
polymer material backbone having graft polymerized thereon a monomer(s) of
a soft polymer(s), a polymer having a glass transition temperature (Tg) of
less than 20.degree. C. The blends obtained have improved impact/stiffness
balance while retaining a balance of other properties, as compared to the
properties of said rigid graft copolymer alone or blended with an
unmodified rubber. The blends are useful as stand-alone structural
plastics for injection molding articles and extruded profiles.
According to one embodiment of the present invention, there is provided a
blend which comprises (A) a propylene polymer material grafted with a
polymerizable monomer(s) of a polymer(s) having a Tg greater than
80.degree. C. and (B) a propylene polymer material grafted with a
polymerizable monomer(s) of a polymer(s) having a Tg of less than
20.degree. C.
According to another embodiment of the present invention, there is provided
a blend which comprises (A) a propylene polymer material grafted with a
polymerizable monomer(s) of a polymer(s) having a Tg of greater than
80.degree. C.; (B) a propylene polymer material grafted with a
polymerizable monomer(s) of a polymer(s) having a Tg less than 20.degree.
C.; and (C) at least one other rubber modifier, wherein the total amount
of (B)+(C) is from 10 to 70%, by weight, of the total blend.
DETAILED DESCRIPTION OF THE INVENTION
Unless otherwise specified all percentages and parts are by weight in this
specification.
The propylene polymer material backbone of component (A) and (B) can be the
same or different and are (i) a homopolymer of propylene, (ii) a random
copolymer of propylene and an olefin selected from ethylene and C.sub.4
-C.sub.10 alpha-olefins, provided that, when the olefin is ethylene, the
maximum polymerized ethylene content is about 10%, preferably about 4%,
and when the olefin is a C.sub.4 -C.sub.10 alpha-olefin, the maximum
polymerized content thereof is about 20%, preferably about 16%, or (iii) a
random terpolymer of propylene with two alpha-olefins selected from the
group consisting of ethylene and C.sub.4 -C.sub.8 alpha-olefin, provided
that the maximum polymerized C.sub.4 -C.sub.8 alpha-olefin content is
about 20%, preferably about 16%, and when ethylene is one of said
alpha-olefins, the maximum polymerized ethylene content is about 5%,
preferably about 4%. The C.sub.4 -C.sub.10 alpha-olefins include linear or
branched C.sub.4 -C.sub.10 alpha-olefins such as 1-butene, 1-pentene,
4-methylpentene-1 , 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene,
1-heptene, 3-methyl-1 - hexene and the like.
Preferred propylene polymer material backbones are polypropylene and
ethylene/propylene random copolymer.
The propylene polymer material of component (A) has grafted thereto
polymerizable monomer(s) of a rigid polymer(s) having a Tg greater than
80.degree. C. Suitable monomer(s) are styrene, styrene/methyl
methacrylate, styrene/methacrylic acid, styrene/maleic anhydride,
styrene/acrylonitrile, styrene/methyl methacrylate/acrylonitrile,
styrene/methyl methacrylate/maleic anhydride and
styrene/acrylonitrile/maleic anhydride.
Preferred grafting monomers are styrene, styrene/methyl methacrylate,
styrene/methacrylic acid and styrene/acrylonitrile.
Component (B) is a propylene polymer material having grafted thereto
polymerizable monomer(s) of a rubbery polymer(s) having a Tg less than
20.degree. C. Examples of said monomers include butyl acrylate, ethylhexyl
acrylate, butyl acrylate/butyl methacrylate, butyl acrylate/ethylhexyl
acrylate and ethylhexyl acrylate/butyl methacrylate. Preferred is butyl
acrylate and butyl acrylate/butyl methacrylate.
Suitable particulate forms of the grafted propylene polymer material
include powder, flake, granulate, spherical, cubic and the like. Spherical
particulate forms prepared from a propylene polymer material having a pore
volume fraction of at least about 0.07 are preferred.
Most preferred for preparing the grafted propylene polymer materials is a
propylene polymer material having (1) a weight average diameter of about
0.4 to 7 mm, (2) a surface area of at least 0.1 m.sup.2 /g, and (3) a pore
volume fraction of at least about 0.07 wherein more than 40% of the pores
in the particle have a diameter larger than 1 micron. Such propylene
polymer materials are commercially available from HIMONT Italia S.r.l.
The grafted propylene polymer material of components (A) and (B) of the
present invention are prepared by the free radical-initiated graft
polymerization of at least one monomer as set forth above, at free radical
sites on propylene polymer material and olefin rubber material. The free
radical sites may be produced by irradiation or by a free radical
generating chemical material, e.g., by reaction with a suitable organic
peroxide.
According to the method where the free radical sites are produced by
irradiation, the propylene polymer material, preferably in particulate
form, is irradiated at a temperature in the range of about 10.degree. to
85.degree. C. with high-energy ionizing radiation to produce free radical
sites in the propylene polymer material. The irradiated propylene polymer
material, while being maintained in a substantially non-oxidizing
atmosphere, e.g., under inert gas, is then treated at a temperature up to
about 100.degree. C. for a period of at least about 3 minutes, with about
from 5 to 80% of the particular grafting monomer or monomers used, based
on the total weight of propylene polymer material and grafting monomer(s).
After the propylene polymer material has been exposed to the monomer for
the selected period of time, simultaneously or successively in optional
order, the resultant grafted propylene polymer material, while still
maintained in a substantially non-oxidizing environment, is treated to
deactivate substantially all of the residual free radicals therein, and
any unreacted grafting monomer is removed from said material.
The free radical deactivation of the resulting graft copolymer is conducted
preferably by heating, although it can be accomplished by the use of an
additive, e.g., methylmercaptan, that functions as a free radical trap.
Typically the deactivation temperature will be at least 110.degree. C.,
preferably at least 120.degree. C. Heating at the deactivation temperature
for at least 20 minutes is generally sufficient.
Any unreacted grafting monomer is removed from the graft copolymer, either
before or after the radical deactivation, or at the same time as
deactivation. If the removal is effected before or during deactivation, a
substantially non-oxidizing environment is maintained.
In the method where the free radical sites are produced by an organic
chemical compound, the organic chemical compound, preferably an organic
peroxide, is a free radical polymerization initiator which has a
decomposition half-life of about 1 to 240 minutes at the temperature
employed during the treatment. Suitable organic peroxides include acyl
peroxides, such as benzoyl and dibenzoyl peroxides; dialkyl and aralkyl
peroxides, such as di-tert-butyl peroxide, dicumyl peroxide, cumyl butyl
peroxide, 1,1-di-tert-butylperoxy-3,5,5-trimethyl-cyclohexane,
2,5-dimethyl-2,5-ditert-butylperoxyhexane, and
bis(alpha-tert-butylperoxyisopropylbenzene); peroxy esters, such as
tert-butylperoxypivalate, tert-butyl perbenzoate,
2,5-dimethylhexyl-2,5-di(perbenzoate), tert-butyl-di(perphthalate),
tert-butyl peroctoate; and 1,1-dimethyl-3- hydroxybutyl-peroxy-2-ethyl
hexanoate; and peroxy carbonates, such as di(2-ethylhexyl) peroxy
dicarbonate, di(n-propyl)peroxy dicarbonate, and di(4-tert-butyl-
cyclohexyl)peroxy dicarbonate. The peroxides can be used neat or in a
diluent medium, having an active concentration of from 0.1 to 6.0 parts
peroxide per 100 parts polypropylene, preferably from 0.2 to 3.0 pph.
According to this method, the propylene polymer material, preferably in
particulate form, at a temperature of from about 60.degree. C. to
125.degree. C. is treated with from 0.1 to 6.0 pph of a free radical
polymerization initiator described above. The polymer material is treated
with about 5 to 240 pph of a grafting monomer at a rate of addition that
does not exceed 4.5 pph per minute at all addition levels of 5 to 240 pph
of the monomer, over a period of time which coincides with, or follows,
the period of treatment with the initiator. In other words, the monomer
and initiator may be added to the heated propylene polymer material at the
same time or the monomer may be added 1) after the addition of the
initiator has been completed, 2) after addition of the initiator has
started but has not yet been completed, or 3) after a delay time or hold
time subsequent to the completion of the initiator addition.
After the propylene polymer material has been grafted, the resultant
grafted propylene polymer material, while still maintained in a
substantially non-oxidizing environment, is treated, preferably by heating
at a temperature of at least 120.degree. C. for at least 20 minutes, to
decompose any unreacted initiator and deactivate residual free radicals
therein. Any unreacted grafting monomer is removed from said material,
either before or after the radical deactivation, or at the same time as
deactivation.
When present, the at least one other rubber modifier, component (C), is
selected from (i) an olefin rubber containing 2 or more monomers selected
from ethylene, propylene or butene, and optionally a non-conjugated diene,
(ii) one or more monoalkenyl aromatic hydrocarbon-conjugated diene block
copolymers or hydrogenated products thereof and (iii) mixtures of (i) and
(ii).
Suitable examples of the olefin rubber of component (C) used in the present
invention are ethylene/propylene copolymer rubber (EPR) having an ethylene
content of from 30 to 70%, ethylene/butene-1 copolymer rubber (EBR) having
an ethylene content of from 30 to 70%, propylene/butenecopolymer rubber
(PBR) having a butene-1 content of from 30 to 70%,
ethylene/propylene/non-conjugated diene monomer rubber (EPDM) having an
ethylene content of 30 to 70% and diene content of from 1 to 10%,
ethylene/propylene/butene terpolymer rubber (EPBR) having a propylene
content of from 1 to 10% and butene content of from 30 to 70% or a
propylene content of from 30 to 70% and butene content of from 1 to 10%.
Examples of the non-conjugated dienes include 1,4-hexadiene,
ethylidene-norborene and dicyclopentadiene.
The one or more monoalkenyl aromatic hydrocarbon-conjugated diene block
copolymers used in the present invention are linear or branched A-B or
A-B-A types or radial (A-B).sub.n , where n is 3-20, and hydrogenated
products thereof or mixtures thereof, where A is a monoalkenyl aromatic
hydrocarbon polymer block and B is a conjugated diene polymer block.
Typical monoalkenyl aromatic hydrocarbon monomers are styrene, C.sub.1-4
linear or branched alkyl ring-substituted styrene and vinyl toluene.
Suitable conjugated dienes are butadiene and isoprene.
According to the present invention mixtures of the monoalkenyl aromatic
hydrocarbon-conjugated diene block copolymer are selected from the group
consisting of two or more of the monoalkenyl aromatic hydrocarbon
conjugated diene block copolymers, two or more hydrogenated derivatives
thereof, and at least one monoalkenyl aromatic hydrocarbon-conjugated
diene block copolymer and at least one hydrogenated derivative thereof.
The monoalkenyl aromatic hydrocarbon-conjugated diene block copolymers have
a number average molecular weight of from 45,000 to 260,000 wherein the
proportion of the monoalkenyl aromatic hydrocarbon monomer in the
monoalkenyl aromatic hydrocarbon-conjugated diene block copolymer ranges
from 5 to 50%, preferably from 15 to 40%, and more preferably from 25 to
40%. When a mixture is used, two or more block copolymers or hydrogenated
products thereof in various amounts and types can be used.
The monoalkenyl aromatic hydrocarbon-conjugated diene block copolymers and
their derivatives used in the composition of the present invention are
commerically available. The linear block copolymers are preferred.
The block copolymers can be synthesized according to the methods in U.S.
Pat. Nos. 3,459,830 and 3,994,856. The method for hydrogenation of the
conjugated diene is also known in the art. The hydrgenation catalyst which
can be used includes noble metal catalyst, such as platinum, nickel
catalyst and copper-chromium catalyst. Specific examples of the methods
for hydrogenation are described in U.S. Pat. No. 4,188,432.
Preferably component (C) is an ethylene/ propylene copolymer rubber, an
ethylene/propylene/non-conjugated diene monomer rubber and a hydrogenated
styrene/butadiene/styrene block copolymer.
The grafted copolymer of propylene polymer material, component (A) is
present in the amount of from 30 to 90%, preferably from 45 to 80%, based
on the total blend. The grafted propylene polymer material has from 5 to
70% of the monomer(s) graft polymerized thereto, and preferably from 20 to
55%.
The grafted copolymer of component (B) is present in the amount of from 10
to 70%, preferably from 20 to 55%, based on the total blend. The grafted
propylene polymer material has from 5 to 50% of the monomer graft
polymerized thereto, and preferably from 10 to 45%.
In the blends of the present invention which contain component (C), the
total amount (B) +(C) is from 10 to 70%, by weight of the total blend,
preferably from 20 to 55%, wherein component (B) is present in an amount
of from 5 to 50%, preferably from 15 to 45% and component (C) is present
in an amount of from 5 to 20%, preferably from 5 to 10%.
Up to about 80 parts (total) of additives such as fillers, reinforcing
agents, etc., per 100 parts of the components (A) and (B) or (A), (B) and
(C) can be included in the blend. In addition, the blend may contain about
from 5 to 30 parts of a propylene polymer material per 100 parts of the
(A) and (B) or (A), (B) and (C), wherein suitable propylene polymer
materials are as set forth herein for the propylene polymer material
useful in preparing the graft copolymer.
The blends of the present invention are prepared by mechanically blending
the components in conventional mixing equipment, i.e., a single or twin
screw extruder, Banbury mixer or any other conventional melt compounding
equipment. The order in which the components of the blend are mixed is not
critical.
The present invention will be illustrated in greater detail with reference
to the examples of the invention set forth below.
Examples 1-5 and Control Examples A-E
The blends of this invention are produced by a general procedure comprising
tumble blending components (A) and (B), and optionally component (C) as
set forth in Table I, and a stabilizing package consisting of 0.07%
Sandostab P-EPQ stabilizer, 0.07% Irganox 1010 stabilizer and 0.25% DSTDP
distearylthiodipropionate, until a homogeneous mixture is obtained
(approximately 1 minute). The mixture of Examples 1 and 2 were extruded at
475.degree. F. and 100 rpm in a vacuum vented, tapered, counter-rotating,
intermeshing twin screw extruder manufactured by Haake. The mixtures of
Examples 3-5 and Control Examples A-E were extruded at 446.degree. F. and
375 rpm with a polymer feed rate of 35 lbs/hr in a vacuum vented, tapered,
co-rotating, intermeshing twin screw extruder manufactured by Leistritz.
The compounded mixture was injection molded in a 1.5 ounce, 25 ton
Battenfeld injection molding machine with a barrel temperature of
450.degree. F. and mold temperature of 140.degree. F. The molding cycle
for the tensile and flex bars consisted of a 10 second injection time, 20
second cooling time, and 2 second mold open time, with a maximum injection
speed (15 setting) and a screw speed setting of 2.
The physical properties set forth in the Tables were measured by the
following methods:
______________________________________
Tensile Strength
ASTM D-638 (using a 2 in/min. crosshead
without extensometer)
Break Elongation
ASTM D-638
Yield Elongation
ASTM D-638
Flexural Modulus
ASTM D-790 and D-618, Procedure A
(0.5 in/min. crosshead speed and
center section of a molded T-bar)
Flexural Strength
ASTM D-638, Procedure A (center
section of a molded T-bar)
Notched Izod
ASTM D-256-87
Weldline Strength
ASTM D-638
______________________________________
TABLE I
__________________________________________________________________________
Examples Control
Ingredients
1 2 3 4 5 A B C D E
__________________________________________________________________________
PP-g-PS.sup.1
43
63
-- -- -- -- -- -- -- --
PP-g-PS.sup.2
-- -- 74
63
74
100 85 80 85 80
PP-g-BA.sup.3
57
-- -- -- -- -- -- -- -- --
PP-g-BA.sup.4
-- 32
-- -- -- -- -- -- -- --
PP-g-BA.sup.5
-- -- 16
32
16
-- -- -- -- --
EP306P.sup.6
-- -- -- 5
10
-- -- -- 15 20
Kraton G-1652.sup.7
-- 5
10
-- -- -- 15 20 -- --
Ten. Str, psi
4386
4365
4457
4142
4165
6295 4208
4082
4017
3273
Flex. Mod, kpsi
241
247
200
218
228
342 187
188.4
246
200
Flex. Str, psi
7228
7621
6497
6600
6751
10,600
6156
6094
6827
5,500
Yield Elong., %
12.4
14.3
23.4
16.2
14.5
10.1 27.2
29.0
10.7
11.6
Break Elong., %
79.0
81.9
71.5
79.1
71.8
18.1 88.8
102
54.1
34.1
N. Izod, ft-lb/in
3.4
3.1
3.1
2.4
2.4
0.17
2.74
3.72
1.8
3.06
__________________________________________________________________________
.sup.1 Polypropylene (5 dg/10 min MFR, 0.35 cc/g porosity) grafted with
styrene, 46% styrene content, 2 parts of (parts of tbutyl peroctoate/100
parts polypropylene) active peroxide, grafting temp. 120.degree. C.,
styrene 85 pph, feed rate 1 pph/min for 85 min., deactivation at
135.degree. C. for 240 min. produced by the premixed addition of peroxide
and monomer polymerization method set forth herein.
.sup.2 Polypropylene grafted with stryene, 46% styrene content, 2 parts o
(parts of tbutyl peroctoate/100 parts polypropylene) active peroxide,
grafting temp. 115.degree. C., styrene 85 pph, feed rate 1 pph/min for 85
min., deactivation at 135.degree. C. for 240 min. produced by the premixe
addition of peroxide and monomer polymerization method set forth herein.
.sup.3 Polypropylene (4.8 dg/10 min. MFR, 0.35 cc/g porosity) grated with
butyl acrylate, 31% butyl acrylate content, 0.5 parts of (parts of tbutyl
peroxyvialate/100 parts polypropylene) active peroxide, grafting temp.
80.degree. C., butyl acrylate 45 pph, feed rate 1 pph/min. for 50 min.,
deactivation at 120.degree. for 35 min. produced by the separate
sequential addition of peroxide and monomer polymerization method set
forth herein.
.sup.4 Polypropylene (4.8 dg/10 min MFR, 0.35 cc/g porosity) grafted with
butyl acrylate, 30.5% butyl acrylate content, 0.5 parts of (parts of
tbutyl peroxypivalate/100 parts polypropylene) active peroxide, grafting
temp. 80.degree. C., butyl acrylate feed 44 pph, feed rate 1 pph/min. for
50 min., deactivation at 120.degree. C. for 30 min. produced by the
separate, sequential addition of peroxide and monomer polymerization
method set forth herein.
.sup.5 Polypropylene (4.8 dg/10 min MFR, 0.35 cc/g porosity) grafted with
butyl acrylate, 31% butyl acrylate content, 0.5 parts of (tbutyl
peroxypivalate/100 parts polypropylene) active peroxide, grafting temp.
80.degree. C., butyl acrylate feed 50 pph, feed rate 1 pph/min. for 50
min., deactivation at 120.degree. C. for 30 min. produced by the separate
sequential addition of peroxide and monomer polymerization method set
forth herein.
.sup.6 Ethylene/propylene copolymer rubber having 57% ethylene,
commercially available from Polysar.
.sup.7 Hydrogenated styrene/butadiene/styrene triblock copolymer produced
by Shell Chemical Co. (29% styrene content, 71% rubber).
Examples 6-7 and Control Example F
The blends set forth in Table II were prepared according to the general
procedure used for the blends of Examples 1 and 2 in Table I, except that
a butyl acrylate/butyl methacrylate grafted polypropylene was used instead
of the butyl acrylate grafted polypropylene.
TABLE II
______________________________________
Examples Con. Ex.
Ingredients 6 7 F
______________________________________
PP-g-PS.sup.1 49 50 100
PP-g-BA/BMA.sup.2
51 -- --
PP-g-BA/BMA.sup.3
-- 50 --
Notched Izod, ft*lb/in
2.5 2.5 0.17
Tensile Strength, psi
4319 4437 6295
Flex Modulus, kpsi
234 238 342
Flex Strength, psi
7184 7374 10,600
Yield Elong., %
11.8 11.1 10.1
Break Elong., %
62.8 54.7 18.1
______________________________________
.sup.1 Polypropylene (5 dg/10 min MFR, 0.35 cc/g porosity) grafted with
styrene, 46% styrene content, 2 parts of (parts of tbutyl peroctoate/100
parts polypropylene) active peroxide, grafting temp. 115.degree. C.,
styrene 85 pph, feed rate 1 pph/min for 85 min., deactivation at
135.degree. C. for 240 min. produced by the premixed addition of peroxide
and monomer polymerization method set forth herein.
.sup.2 Polypropylene (4.8 dg/10 min MFR, 0.35 cc/g porosity) grafted with
butyl acrylate/butyl methacrylate (BA/BMA), (3.6:1 wt ratio), 29.5% BA/BM
content, 0.4 parts of (parts of tbutyl peroxypivalate/100 parts
polypropylene) active peroxide, grafting temp. 80.degree. C., BA/BMA 42
pph, feed rate 1.3 pph/min for 38 min., deactivation at 120.degree. C. fo
60 min. produced by the premixed addition of peroxide and monomer
polymerization method set forth herein.
.sup.3 Polypropylene (4.8 dg/10 min MFR, 0.35 cc/g porosity) grafted with
butyl acrylate/butyl methacrylate, (BA/BMA), (8:1 wt ratio), 30.5% BA/BMA
content, 0.5 parts active peroxide, (parts of tbutyl peroxypivalate/100
parts polypropylene), grafting temp. 80.degree. C., BA/BMA 44 pph, feed
rate 1.3 pph/min for 38 min., deactivation at 120.degree. C. for 60 min.
producd by the premixed addition of peroxide and monomer polymerization
method set forth herein.
Examples 8-15 and Control Examples G-K
The blends set forth in Table III were prepared according to the general
procedure used for the blends in Table I, except that a
styrene/acrylonitrile grafted polypropylene was used instead of the
styrene grafted polypropylene. Examples 8 and 9 were extruded according to
Example 1 and Examples 10-15 and Control Examples G-K were extruded
according to Example 3 of Table 1.
Examples 16-18 and Control Example L
The blends set forth in Table IV were prepared according to the general
procedure used for the blends in Table I, except that a styrene/methyl
methacrylate grafted polypropylene was used instead of the styrene grafted
polypropylene. Example 16 was extruded according to Example 1 and Examples
17 and 18 and Control Example L were extruded according to Example 3.
TABLE III
__________________________________________________________________________
Examples Controls
Ingredients
8 9 10 11 12 13 14 15 G H I J K
__________________________________________________________________________
PP-g-PSAN.sup.1
57
43
-- -- -- -- -- -- -- -- -- -- --
PP-g-PSAN.sup.2
-- -- 52
36
74
63
74
63
100
85 80
85
80
PP-g-BA.sup.3
43
57
-- -- -- -- -- -- -- -- -- -- --
PP-g-BA.sup.4
-- -- 48
64
16
32
16
32
-- -- -- -- --
EP306P -- -- -- -- -- -- 10
5
-- -- -- 15
20
Kraton G-1652
-- -- -- -- 10
5
-- -- -- 15 20
-- --
Ten. Str, psi
3766
3532
3657
3303
4000
3856
3846
3737
5737
3970
3550
3654
3049
Flex. Mod, kpsi
243
221
184
165
194
184
203
200
339
193
169
218
181
Flex. Str, psi
6848
6159
5534
4985
6082
5714
5867
5795
9934
6048
5350
5927
4883
Yield Elong, %
13.7
14.0
18.8
19.4
18.9
19.9
16.7
18.4
9.78
19.0
20.1
14.0
14.4
Break Elong, %
20.6
23.9
101
729
71.7
92.0
53.5
80.9
18.9
58.0
95.1
58.8
54.9
N. Izod, ft-lb/in
0.8
1.2
1.5
2.1
1.3
1.4
1.4
1.2
0.21
1.73
2.3
2.6
3.6
__________________________________________________________________________
.sup.1 Polypropylene grafted with styrene/acrylonitrile (SAN) (3:1 wt
ratio), 46% styrene/acrylonitrile content, 1.2 parts of (parts of tbutyl
peroctoate/100 parts polypropylene) active peroxide, grafting temp.
120.degree. C., SAN 85 pph, feed rate 1 pph/min for 85 min., deactivation
at 140.degree. C. for 120 min. produced by the premixed addition of
peroxide and monomer polymerization method set forth herein.
.sup.2 Polypropylene grafted with styrene/acrylonitrile (SAN) (3:1 wt
ratio), 46% SAN content, 1.6 parts of (parts of tbutyl peroxypivalate/100
parts polypropylene) active peroxide, grafting temp. 90.degree. C., SAN 8
pph, feed rate 1 pph/min for 85 min. deactivation at 90.degree. C. for 12
min. produced by the premixed addition of peroxide and monomer
polymerization method set forth herein.
.sup.3 Polypropylene grafted with butyl acrylate (BA), 31% butyl acrylate
content, 0.5 parts of (parts of tbutyl peroxypivalate/100 parts
polypropylene) active peroxide, grafting temp. 80.degree. C., BA 45 pph,
feed rate 1 pph/min. for 50 min., deactivation at 120.degree. C. for 35
min. produced by the separate, sequential addition of peroxide and monome
polymerization method set forth herein.
.sup.4 Polypropylene grafted with butyl acrylate (BA), 31% butyl acrylate
content, 0.5 parts of (parts of tbutyl peroxypivalate/100 parts
polypropylene) active peroxide, grafting temp 80.degree. C., BA 50 pph,
feed rate 1 pph/min, for 50 min, deactivation at 120.degree. C. for 30
min. produced by the peroxide method set forth herein.
TABLE IV
______________________________________
Examples Con. Ex.
Ingredients 16 17 18 L
______________________________________
PP-g-PSMMA.sup.1
57 -- -- --
PP-g-PSMMA.sup.2
-- 52 36 100
PP-g-BA.sup.3 43 -- -- --
PP-g-BA.sup.4 -- 48 64 --
Ten. Str, psi 5007 4450 3935 6930
Flex. Mod, kpsi
246 226 195 358
Flex. Str, psi
7947 7118 5986 11830
Yield Elong, %
14 16.6 17.9 11.7
Break Elong, %
60 95.8 193 25.7
N. Izod, ft-lb/in
1.6 1.1 1.8 0.2
______________________________________
.sup.1 Polypropylene (9 dg/10 min MFR, 0.53 cc/g porosity) grafted with
styrene/methyl methacrylate (SMMA) (1.8:1 wt ratio), 46% styrene/methyl
methacrylate content, 1.65 parts of (parts tertbutyl peroctoate/100 parts
polypropylene) active peroxide, grafting temp. 100.degree. C., SMMA 86
pph, feed rate 1.25 pph/min. for 67 min., deactivation at 120.degree. C.
for 120 min., produced by the preaddition of peroxide and monomer
polymerization method set forth herein.
.sup.2 Polypropylene (5 dg/10 min MFR, 0.35 cc/g porosity) grafted with
styrene/methyl methacrylate (SMMA) (1:0.52 wt. ratio), 41% SMMA content,
1.2 parts of (parts tertbutyl peroctoate/100 parts polypropylene) active
peroxide, grafting temp. 100.degree. C., SMMA 1 pph, feed rate 1 pph/min.
for 70 min., deactivation at 140.degree. C. for 120 min., produced by the
premixed addition of peroxide and monomer polymerization method set forth
herein.
.sup.3 Polypropylene (4.8 dg/10 min MFR, 0.35 cc/g porosity) grafted with
butyl acrylate (BA), 31% butyl acrylate content, 0.5 parts of (parts of
tbutyl peroxypivalate/100 parts polypropylene) active peroxide, grafting
temp 80.degree. C., butyl acrylate 45 pph, feed rate 1 pph/min. for 50
min., deactivation at 120.degree. C. for 35 min. produced by the separate
sequential addition of peroxide and monomer polymerization method set
forth herein.
.sup.4 Polypropylene (4.8 dg/10 min MFR, 0.35 cc/g porosity) grafted with
butyl acrylate (BA), 31% butyl acrylate content, 0.5 parts of (parts of
tbutyl peroxypivalate/100 parts polypropylene) active peroxide, grafting
temp 80.degree. C., butyl acrylate 50 pph, feed rate 1 pph/min. for 50
min., deactivation at 120.degree. C. for 30 min. produced by the peroxide
method set forth herein.
Other features, advantages and embodiments of the invention disclosed
herein will be readily apparent to those exercising ordinary skill after
reading the foregoing disclosures. In this regard, while specific
embodiments of the invention have been described in considerable detail,
variations and modifications of these embodiments can be effected without
departing from the spirit and scope of the invention as described and
claimed.
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